IE43247B1

IE43247B1 - Piperidyl-triazine derivatives

Info

Publication number: IE43247B1
Application number: IE1369/76A
Authority: IE
Original assignee: Chimosa Chimica Organica Spa
Priority date: 1975-12-18
Filing date: 1976-06-23
Publication date: 1981-01-14
Also published as: ES454370A1; DE2636130C3; AT351269B; US4108829A; ATA931176A; US4263434A; FR2335509B1; JPS5273886A; BE847034A; NL7610695A; NL166940C; JPS5738589B2; FR2335509A1; NL166940B; CH632523A5; LU75880A1; IE43247L; GB1511773A; DK167017B1; DE2636130A1

Abstract

1511773 Piperidyl - triazine derivatives CHIMOSA CHIMICA ORGANICA SpA 29 June 1976 [18 Dec 1975] 27110/76 Heading C2C [Also in Division C3] Novel piperidyl-triazine derivatives of the formula wherein R 1 and R 2 are the same or different and each is hydrogen, hydroxyl, straight or branched chain C 1 to C 18 alkyl, C 5 to C 18 cyoloalkyl, substituted or unsubstituted C 6 to C 18 aryl, C 7 to C 18 aralkyl, a piperidine radical of Formula (II) in which R 4 , R 5 , R 7 and R 8 are the same or different and each is C 1 to C 6 alkyl and R 6 is H, -O, C 1 to C 12 alkyl, or C 2 to C 12 alkenyl or alkynyl, or R 1 and R 2 may be in which R 9 and R 10 are the same or different and each is hydrogen, C 1 to C 8 alkyl, C 5 to C 8 cycloalkyl, or C 6 to C 8 aryl; X and Y are the same of different and each is -O-, -S-, or R 11 being H, straight or branched chain C 1 to C 18 alkyl, C 5 to C 18 cycloalkyl, C 6 to C 18 aryl, C 7 to C 18 aralkyl or a piperidine radical of Formula (II); R 1 -X- and R 2 -Y-, taken as a single substitutent group, may be a radical of a nitrogenous heterocyclic compound having 5 to 8 ring atoms linked to the triazine ring by means of a disubstituted nitrogen atom of said radical, or R 1 -X- and R 2 -Y- may be Cl- or Br-; n is an integer from 2 to 6; R 3 is an n-valent residue derived from a polyalcohol, a polymercaptan or a polyamino by reaction of the active H atoms thereof with a halogen atom of a monohalo triazine; or R 3 may be R 12 -(Z)- n , where R 12 is an n-valent C 1 to C 18 aliphatic, C 5 to C 18 cycloaliphatic or C 6 to C 18 aromatic radical, and Z is -O-, -S- or R 11 being as defined above; n=2, radical R 3 may be a divalent radical of a nitrogenous heterocyclic compound having 6-8 ring atoms, the disubstituted nitrogen atoms of which are linked to a triazine ring; when n = 2, radical R 3 may be in which R 13 and R 14 are the same or different, and each is hydrogen, C 1 to C 12 alkyl, C 5 to C 12 cycloalkyl, C 6 to C 12 aryl, C 7 to C 12 aralkyl, or a piperidine radical of Formula (II); when n = 3 4, 5, or 6, R 3 may be wherein R 11 is as defined above, r and s are the same or different and each is an integer from 2 to 6, and t is 0,1,2 or 3 provided that at least one piperidine radical of Formula (II) is present in at least one of the radicals R 1 -X-, R 2 -Y-, and R 3 , are prepared by reacting a 4,6-disubstituted-2-halotrizine or a 6-substituted- 2,4-dihalotriazine with the appropriate polyalcohol, polymercaptan or polyamine in an inert solvent at elevated temperature and in the presence of an organic or inorganic base. The novel compounds may be used as light stabilizers for organic polymers. The triazine starting material may be prepared by reacting cyanuric chloride with an appropriate amine.

Description

The present invention related to piperidyl-triazine derivatives which are useful for improving the stability to light, heat and oxidation of polymeric substances.

• It is knpwn that synthetic polymers are liable to 5 undergo a severedeterioration of .their physical and chemical properties when they are exposed to sunlight or other ultraviolet light source.

In order to improve the stability to light of said synthetic polymers, various stabilizers have been proposed, some of which have found a wide commercial acceptance in the field, such as some benzophenones, bertzotriazoles, aromatic salicylates, α-cyanoacrylic acid esters, organo-tin compounds ahd the like which although having a certain efficiency level, are not successful to solve the problem - I ’ ' ' completely.

It is further known that some piperidine derivatives of 1,3,5'triazine can be used to protect a polymeric material from degradation due to ultraviolet light.

In particular, French Patent No. 2 181 059 describes triazine compounds having the general formula 324? wherein Z1, Z, Z’ can be, among others, piperidine radicals of the formula A A οη3Ζ\η3 in which X is -0- or -NH-. ub The above products considerably improve the light stability of polyolefins, but they are of poor utility in the application to an article of small thickness, such as fibers and films, inasmuch as they tend to be extracted by contact with water or aqueous solutions of surfactants, the stabilizer amount remaining in the polymer being no longer sufficient to provide the required light stabilization.

On the other hand the usual commercial light stabilizers, such as benzophenone derivatives, have a reduced effect on light stabilization in polyolefins, when used in articles of small thickness, such as fibers and films.

Therefore there is a need for more efficient light stabilizers for protection against the polymer degradation due to UV light, as well as stabilizers resistant to extraction from the polymer.

According to the present invention, there is provided a compound having the formula (I): wherein R-| and R2 are the same or different and each is hydrogen, hydroxyl, straight or branched chain C-j to C-jg (preferably c1_cio) sHyl, c5_ci3 (preferably C5-Cl0) cycloalkyl, substituted or unsubstituted Cg to C-jg (preferably Cg-C10) aryl, Cy to C^g aralkyl, or a piperidine radical of formula (II) (Π) in which R4, Rg, Ry and Rg are the same or different, and each is C·] to Cg alkyl (preferably methyl) and Rg is H, 0, a C-| to C-j2 alkyl (preferably methyl), or C2 to C^2 alkenyl or alkynyl; or R-j and R2 may be -f-Rio Rg in which Rg and R^ are the same or different and each is hydrogen, to Cg alkyl (preferably methyl), C5 to Cg cycloalkyl, or Cg to Cg aryl; X and Y are the same or different and each is -0-, -S- or -NI Rn R]·] being -H, straight or branched chain C-j to Clg (preferably Ci-c^q) alkyl, Cg to C^g (preferably Cg-C10) cycloalkyl, Cg to Clg (preferably Cg-C^) aryl, Cy to C^g aralkyl, or a piperidine radical of formula (II); the radicals R^-X- and R2-Y-, taken as a single substituent group, may be a radical of a nitrogenous heterocyclic compound having 5 to 8 ring atoms linked to the triazine ring by means of a disubstituted nitrogen atom of said radicals, or R^-X- and R2-Y- may be Cl- or Br-; n is an integer from 2 to 6; Rg is an n-valent residue derived from a polyalcohol, a polymercaptan or a polyamine by reaction of the active H atoms thereof with a halogen atom of a monohalo triazine; or Rj may be R12 -(Z)n-, wherein R]2 is an n-valent Cj to C18 aliphatic, Cg to C18 cycloaliphatic or Cg to Clg aromatic radical, and Z is -0-, -S- , or - Ν I Rn wherein R^ is as defined above; when n=2, the radical Rg may be a divalent radical of a nitrogenous heterocyclic compound having 6 to 8 ring atoms, the disubstituted nitrogen atoms of which are linked to a triazine ring; when n = 2, Rg may be — N —N 1 I R13 R14 in which Rjg and R^ are the same or different and each is hydrogen, C-j to C^2 alkyl (e.g. methyl), Cg to C-j2 cycloalkyl, Cg to C^2 aryl, Cy to C^2 aralkyl or a piperidine radical of formula (II); when n = 3, 4, 5, or 6, then Rg may be -NHC^VN-QCH^-N^ (CH2)r-NRn Rn in which R^ is as defined above; r and s are the same or different and each is an integer from 2 to 6, and t is 0, 1, 2 or 3, lb provided that at least one piperidine radical of formula (II) is present in at least one of the radicals R-j-Χ-, Rz-Y-, and Rg. 32 4 7 Also according to the present invention, there is provided a method of producing a compound of the formula (I) as defined above, comprising reacting a 4,6-disubstituted 2-halogen-triazine with a polyalcohol, a polymercaptan or a polyamine in an inert solvent, at the boiling temperature of the solvent, in the presence of an organic or inorganic base, to form the corresponding compound, and recovering said compound from the mixture.

Also according to the present invention, there is provided a method of producing a compound of the formula (I) as defined above comprising reac.ting a 6-substituted-2,4-diha1ogen-l,3,5triazine with a compound of the formulae RpXH and a compound of the formula Rg-YH, Rp Rg» X and Y being as defined above, in a molar ratio of 1:2 n, in an inert solvent, at the boiling temperature of the solvent, in the presence of an organic or inorganic base, to form the corresponding compound, and recovering said compound from the mixture.

Each of R} and Rg may be H, OH, NHg, N(CH3)g, methyl, ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethyl20 cyclohexyl, phenyl, 0-, m-, p-toluyl, 2,6-dimethylphenyl, 2.4.5- trimethylphenyl, a- or g-naphtyl, benzyl, p-methylbenzyl, 2,2,5,6-tetramethyl-5-pi peridyl, 1,2,2,6,6-pentamethyl-4piperidyl or 1-allyl-2,2,6,6-tetramethyl-4-piperidyl.

Rp may be hydrogen, methyl, ethyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3.3.5- trimethylcyclohexyl, phenyl, p-toluyl, benzyl, 2,2,6,6tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl or l-propyl-2,2,6,6-tetramethyl-4-piperidyl.

R-j-X- and R2-Y-, when they represent radicals of nitrogenous heterocyclic compounds having 5 to 8 ring atoms, are preferably 1-pyrrolidinyl, l-piperidinyl, 4-morpholinyl, 4-methyl-1-piperkzinyl or 4-methyl-lhomopiperazinyl.

Rl2 be C-| to C-jg alkylene, Cg to cycloalkylene, Cg to C]o cycloalkylene, Cg to C1Q arylene or C? to C1Q aralkylene.

When n = 2, R^ is preferably methylene, ethylene, 1,2-propylene, trimethylene, hexamethylene, 2,2,4-trimethyl10 hexamethylene, 2,4,4-trimethylhexamethylsne, decamethylene, 1,4-cyclohexylene, 4,41-methylenedicyclohexylene, o*. m- or p-phenylene, or ο-, m- or p-xylylene.

When n = 3, is preferably When n = 4, R^2 is preferably CH? I -CH/- C -CH?I ch2 or -ch2-ch2 N-CH2-CH2-N -ch2-ch2 ch2-ch2ch2-ch2When n = 2, R3 may be a radical of a heterocyclic compound having 6 to 8 members containing 2 nitrogen atoms, such as or it can be substituted by a hydrazine radical such as -NH-NH-, -N — Nl I ch3 ch3 When n = 3, R3 may be a radical from a dialkylenetriamine, such as: -HN-(CH2) 2-fJ-(CH2) 2-NHor I -hn-(ch2)3-n-(ch2)3-nhWhen n = 4, R3 may be a radical from a trialkylenetetramine, such as: 43»· ‘ -HN-(CH2)2-N-(CH2)2 -n-(ch2)2-nhWhen n = 5, R3 may be a radical from a tetraalkyl enepentamine, such as: -hn(ch2-ch2-n-),-ch2-ch2-nhUhen n = 6, R3 may be a radical from a pentaalkylenehexamine, such as: -nh(ch2-ch2-n-)4-ch2-ch2-nhPreferably each of r and s is 2, 3 or 6, t is 0 and n is 2 or 3.

Advantageously, each of X, Y and Z is -0-, >NH, N-alkyl having 1 to 6 carbon atoms, or >N-Pip, Pip being 2,2,6,6-tetramethyl-4-piperidyl; each of R-j and R2 is hydrogen; C-j to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; R4, Rg, · Ry and Rg are methyl; Rg is hydrogen; Rg and RyQ are hydrogen; R-|j is hydrogen, C-j to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; and Ry3 and Ry4 are hydrogen.

Alternatively, each of X, Y and Z is -0-, >NH, >N-alkyT having 1 to 6 C. atoms, >N-Pip, Pip being 2,2,6,6-tetramethyl -4-piperidyi; each of R^ and R2 is hydrogen, Cy to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; R^, Rg, R? and Rg are methyl Rg is hydrogen; Rg and Rjg are hydrogen; R^ is hydrogen, Cj to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; and R-j3 and R14 are hydrogen.

Alternatively, each of X, Y and Z is -0-, >NH, >N-alkyl having 1 to 6 C. atoms, >N-Pip, Pip being 2,2,6,6-tetramethy1-4-piperidyl; each of R-| and R2 is hydrogen, C-| to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; R^, Rg, Ry and Rg are methyl; Rg is hydrogen; Rg and R-j0 are hydrogen; Rll is hydrogen, C^ to Cg alkyl or 2,2,6,6-tetramethyl-4piperidyl; each of r and s is 2 or 3, t is 0, and n is 2 or 3.

The triazine compounds of formula (I) can be prepared by reacting a 4,6-disubstituted-2-halogen-l ,3,5-triazine of formula R.

N.

Cl R, ‘2 (III) with a polyfunctiona! compound of formula (IV) or with a hydrazine of formula HN—NH (V) or with a polyamine of formula (VI) The molar ratio of the reactant of formula (III) to the reactant of formula (IV) is preferably n:l, the molar ratio of the reactant of formula (III) to the reactant of formula (V) is preferably 2:1, the molar ratio of the reactant of formula (III) to the reactant of formula (VI) is preferably one mole of (III) per one amine group of the polyamine (VI); in each case it is possible to employ the reactant of formula (III) in excess to ensure complete reaction.

An alternative process for the preparation of compounds 10 of formula (I) comprises reacting a 6-substituted-2,4-dichloro1,3,5-triazine of formula with a compound having the formula RpXH (VIII) and a compound having the formula R2-YH (IX) In such.a case, the molar ratio of reactants (VIII) and (IX) to dichlorotriazine (VII) is 2n:1, but it is possible to employ an excess of reactants R^XH, R2-YH to assure a complete reaction.

The reactions of halogentriazines (III) or (VII) with the compounds of formula (IV), (V), (VI), (VIII), (IX) respectively are carried out in the presence of inert solvents such as acetone, dioxane, toluene, xylene, at the boiling a temperature of the solvent.

The reactions are carried out in the presence of an organic or inorganic base in order to fix hydrogen halide; there can be used for example: triethylamine, or tri butyl amine sodium hydroxide, carbonate or bicarbonate; potassium hydroxide or carbonate; sodium alcoholates in the case where the compounds of formula (IV) or formulae (VIII) and (IX) are alcohols; sodium mercaptides in the case where the reactants of formula (IV) or formulae (VIII and IX) are mercaptans; it is also possible to use an amine excess in lo the case where a product of formula (VII) is reacted with the compounds of formulae (VIII and IX) in which X and Y represent -NI R11 In order to further illustrate the present invention, some examples of preparation are given in the following for an illustrative and not limitative purpose. 43347 Example Ί A) 2-chloro-4,6-bis(2,6-dimethylphenoxy)-l,3,5-triazine v;as prepared according to the teachings of German Patent Publication No. 2 307 777. 55.3 g (0.3 moles) of cyanuric chloride dissolved in 300 ml of acetone were added within 30 minutes at 20-25°C to a solution of 73.2 g (0.5 moles) of 2,6 dimethyl phenol, g (0.6 moles) of sodium hydroxide and 340 ml of water.

The mixture was stirred for three hours at the same temperature and the precipitate so obtained was removed by filtration, washed, dried and crystallized from petroleum ether; a white powder melting at 159-160°C was obtained.

B) Preparation of N,N‘ - bis(2,2,6,6 - tetramethyl 4 - piperidyl) - N,N‘ - bis - [^2,4 - bis(2,6 - dimethylphenoxy) - 1,3,5 - triazine - 6 - ylj hexamethylene diamine. .5 g (0.1 mole) of 2-chloro-4,6-(bis(2,6-dimethylphenoxy) -1,3,5-triazin, 19.7 g (0.05 moles) of 1,6-bis(2,2,6,6-tetramethyl -4-piperidylami«o)hexane, 4 g (0.1 mole) of sodium hydroxide and 250 ml of xylol were boiled for 16 hours under stirring.

The reaction solvent was removed, the residue was washed with water, dried at l00°C/1 mm and crystallized from anhydrous ethanol.

A white solid melting at 224-229°C, N % = 13.34 (calculated for 062Ηθ4Ν]θ04 = 13.55%) was obtained.

Example 2 A) 2 - chloro - 4,6 - bis(2,2,6,6 - tetramethyl - 4 piperidylamino) - 1,3,5 - triazine was prepared according to the French Patent 2 181 059. 18.45 (0.1 mole) cyanuric chloride, slurried into 600 ml water, were added to 31.2 g (0.2 moles) of 4-amino-2,2,6,6; tetramethylpiperidine and a solution of 8 g (0.2 moles) of sodium hydroxide in 20 ml water. The mixture was stirred for 30 minutes at room temperature, then it was heated to 90°C for 16 hours.

After cooling, the precipitate was removed by filtration, washed and dried under vacuum. A white powder melting at 27/-278°C was obtained.

Preparation of B) N,N‘ - bis 2,4 - bis(2,2,6,6 - tetramethyl - 4 piperidylamino) - 1,3,5 - triazin - 6 - yl hexamethylenediamine; 42.3 (0.1 mole) of 2-chloro-4,6-bis (2,2,6,6-tetramethyl -4-piperidylamino)-l,3,5-triazine, 5.8 g (0.05 moles) of hexamethylenediamine, 4 g (0.1 moles) of sodium hydroxide and 500 ml of xylene were boiled for 16 hours under stirring. After removing the reaction solvent, the residue was washed with water, dried at 100°C/l mm and crystallized from methylethylketone.

A white solid melting at 153-156°C was obtained.

N % = 24.66 (calculated for = 25.16%). 133 47 Example 3 A) Preparation of 2 - chloro - 4,6 - bis - (n-butylamino 1,3,5 - triazine as starting compound: a mixture of 18.45 g (0.1 mole) of cyanuric chloride, 180 ml of acetone and 160 g of ice was added to 14.6 (0.2 moles) of n-butylamine dissolved in 100 ml acetone. The mixture temperature was raised to 30°G, then 8 g (0.2 moles) of sodium hydroxide dissolved in 100 ml of water were added.

The mixture was stirred for 6 hours at 30-35°C, then the precipitate so obtained was filtered, washed with water and dried on anhydrous CaCl2, A white powder melting at 209-212°C was obtained, chlorine % = 13.70 calculated, for CnH2QClfl5 = 13.81%.

B) Preparation of N,N' - bis(2,2,6,6 - tetramethyl - 4 piperidyl) - N,N' - bis - jj?,4 - bis - (n - butylamino) 1,3,5 - triazin - 5 - yljethylene diamine: 51.5 (0.2 moles) of 2 - chloro - 4,6 - bis - n - butylamino - 1,3,5 - triazine, 33.8 g (0.1 mole) of 1,2 - bis(2,2,6,6 tetramethyl - 4 - piperidylamino)ethane, 8 g (0.2 moles) of sodium hydroxide and 500 ml of xylene were boiled for 15 hours under stirring. After removing the reaction solvent, the residue was washed with water, dried at 100°C/l mm and crystallized from methyl-ethyl-ketone.

A white solid melting at 143-45°C was obtained. Ν I = 24.51 (calculated for C42Hg0N14 = 25.12%).

Example 4 Preparation of N,N‘ - bis(2,2,6,6 - tetramethyl - 4 piperidyl) - N,N' - bis-^2,4 - bis(2,2,6,6 - tetramethyl - 4 piperidylamino) - 1,3,5 - triazin - 6 - yljethylenediamine. 21.15 g (0.05 moles) of 2-ch1oro-4,6-bis(2,2,6,6-tetramethyl -4-piperidylamino)-l ,3,5-triazine (prepared according to example 2A), 8.45 g (0.025 moles) of 1,2-bis-(2,2,6,6 - tetramethyl -4-pi per i dyl ami no) ethane, 2 g (0.05 moles) of sodium hydroxide and 150 ml of xylene were boiled for 16 hours under stirring.

After removing the reaction solvent, the residue was washed with water, dried at 100°C/l mm and crystallized from benzene.

A white solid melting at 325-328°C was obtained. N%= 22.14 (calculated for C62H116N18 = 22-bb3;)· Example 5 Preparation of N,N' - bisj_2,4 - bis(2,2,6,6 - tetramethyl - 4 - piperidylamino) - 1,3,5 - triazin - 6 - ylj ethylenediamine. lb 42.3 (0.1 mole) of 2-chloro-4,6-bis(2,2,6,6-tetramethyl -4-piperidylamino)-l,3,5-triazine (prepared according to example 2A), 3 g (0.05 moles) of ethylenediamine, 4 g of sodium hydroxide and 150 ml of xylene were boiled for 16 hours under stirring.

After removing the reaction solvent, the residue was washed with water, dried at 100°C/l mm and crystallized from methanol. A white solid melting at 290-292°C was obtained.

N % = 26.09 (calculated for Ο^Ηθ^θ = 26.83%.

Example 6 A) Preparation of N,N'-bis(2,4-dichloro-1,3,5-triazin -6-yl)piperazine. 36.9 (0.2 moles) of cyanuric chloride dissolved in 200 ml of acetone were added to a solution of 8.6 g (0.1 mole) of anhydrous piperazine in 50 ml of acetone at 0-5° within 30 minutes. It was stirred for 30 minutes at 0-5°C, then a solution of 8 g (0.2 moles) of NaOH in 50 ml of water were added within 30 minutes at the same temperature. It was stirred again for 4 hours at 0-5°C, then it was diluted with 100 ml of ice water, filtered, washed with water and dried on anhydrous CaCl2. A white powder melting at < 300°C was obtained, chlorine % 37.32 (calculated for C-j0H8Cl^Ng = 37.17%).

B) Preparation of N,N‘ - bis (22,4 - bis £n(2,2,6,6 tetramethyl - 4 - piperidyl) - n - butylaminoj - 1,3,5 triazin - 6 - ylj - piperazine. 19.1 g (0.05 moles) of N,N'- bis(2,4 - dichloro - 1,3,5 - triazin - 6 - yl)piperazine, 46.6 g (0.22 moles) of 2,2,6,6 - tetramethyl-4-(n-butyl-amino)piperidine, 80 ml of xylene and 8 g (0.2 moles) of NaOH were heated at reflux temperature for 16 hours. After removing the reaction solvent, the residue was washed with water, dried at 100°C/l mm and crystallized from methyl ethyl ketone.

A white crystalline product melting at 272-275°C was obtained, N % 20.37 (calculated for Cg2H11gN^g.H20 = .32%).

Example 7 A) Preparation of 2 - chloro - 4,6 - bis -^(2,2,6,6 tetramethyl - 4 - piperidyl)-ethyl ami noJ - 1,3,5 - triazine.

A mixture of 92.2 g (0.5 moles) of cyanuric chloride, 500 ml of acetone and 160 g of ice was added to 184 g (1 mole) of 2,2,6,6 - tetramethyl - 4 - ethyl aminopiperidine dissolved in 100 ml of acetone.

The mixture temperature was raised to 35°C, then 40 g (1 mole) of sodium hydroxide dissolved in 100 ml of water were added. The mixture was stirred for 6 hours at 35-40°C, then the precipitate so obtained was filtered, washed with water and dried on anhydrous CaClg· After crystallization from acetone a white crystalline powder melting at 127-1Z9°C was obtained, chlorine % = 7.36 (calculated for CggH^gClNy = 7.40).

B) Preparation of Ν,Ν',Ν - tris[2,4 - bis[N(2,2,6s6 tetramethyl - 4 - piperidyl)ethylamino 1,3,5] - triazin - & yl] -diethylenetriamine. 143.8 g (0.3 moles) of 2 - chloro - 4,6 - bis 20 N(2,2,6,6 - tetramethyl - 4 - piperidyl)ethylamino 1,3,5 triazine, 10.3 g (0.1 mole) of diethylenetriamine, 12 g of sodium hydroxide and 450 ml of xylene were boiled for 16 hours under stirring.

After filtration, the solution was stirred at room 26 temperature with 50 ml of water. A white precipitate, melting at 145-150°C was obtained, N % = 22.78 calculated for CgH-jqN2. HgO - 23.13%).

The piperidyl triazine derivatives of formula (I) are useful and valuable agents for improving the stability to light, heat and oxidation of synthetic polymers such as, for example, high and low density polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinylacetate copolymers, polybutadiene, polyisoprene, polystyrene, styrene-butadiene copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl- and vinylidene chloride polymers and copolymers, polyoxymethylene, polyethylene-terephthalate, nylon 66, nylon 6, nylon 12, polyurethanes, unsaturated polyesters.

The compounds of formula (I) can be employed in a mixture with the synthetic polymers in various proportions, depending on the polymer nature, final use and presence of additional additives.

Generally it is preferable to employ from 0.01 to 5% by weight of compounds of formula (I) referred to the polymer weight, more preferably from 0.1 to 1%.

The compounds of formula (I) can be included in a polymeric material composition by various procedures, such as dry mixing in the form of powder, or by a wet process in the form of a solution or slurry. In said operation the synthetic polymer can be employed in the form of powder, granulate, solution, slurry or emulsion.

The polymers stabilized by the products of formula (I) can be used for the manufacture of moulded articles, films, tapes, fibers and monofilaments. 43347 A mixture of compounds of formula (I) and synthetic polymers can be optionally additioned with other additives, such as antioxidants, UV absorbers, nickel stabilizers, pigments, charges, plastifying agents, antistatic agents, flame retardants, lubricating agents, anticorrosive agents and metal inhibitors.

Particular examples of additives which can be employed in a mixture with the compounds of formula (I) are: phenolic antioxidants, such as 2,6 - ditert - butyl - p - cresol, 4,4' - thiobis-(3 - methyl - 6 - tertbutyl phenol), 1,1,3 - tris -(2- methyl - 4 - hydroxy - 5 - tertbutyl phenyl) butane, octadecyl - 3 - (3,5 - ditertbutyl - 4 hydroxyphenyl)propionate, pentaerythritol - tetra - (3,5 - ditert - butyl - 4 - hydroxyphenyl) - propionate, trislb (3,5 - ditert - butyl - 4 - hydroxyhenzyl)isocyanurate; esters of thiodipropionic acid, such as di - n dodecyl - thiodipropionate, di - n - octadecyl - thiodipropionate, aliphatic sulfides and disulfides, such as di - n - dodecylsulfide, di - n - octadecyl - sulfide, di - n - octadecyl - disulfide; aliphatic, aromatic or aliphatic - aromatic phosphites and thiophosphites, such as tri - n - dodecyl - phosphite, tris - (n - nonylphenyl)phosphite, tri - n - dodecyl - trithiophosphite, phenyl - di - n - decylphosphite, di - n - octadecylpentaerythritoldiphosphite; UV absorbers such as 2 - hydroxy - 4 - n octyloxybenzophenone, 2 - hydroxy - 4 - n - dodecyloxybenzophenone, - (2* - hydroxy - 3',5' - ditert - butyl phenyl)5 chlorobenzotriazole, 2 - (2' - hydroxy - 3',5' - di - tert amylphenyl)benzotriazole, 2,4 - ditertbutyl phenyl - 3,5 - di - tertbutyl - 4 - hydroxybenzoate, phenyl - salicylate, p-tert - butylphenyl - salicylate, 2,2* - dioctyToxy 5,5* - ditertbutyloxam'l ide, 2 - ethoxy - 5 - tert - butyl 2' - ethyloxanilide; nickel stabilizers such as Ni monoethyl - 3,5 ditertbutyl - 4 - hydroxybenzylphosphonate, butylamine Ni 2,2' - thiobis -(4- tertoctyl phenol ate) complex, Ni 2,2* - thio - bis -(4- tertoxtylphenolphenolate) Ni dibutyldithiocarbamate, Ni 3,5 - ditertbutyl - 4 hydroxybenzoate, Ni complex of 2 - hydroxy - 4 - n octyloxybenzophenone; organo-tin compounds, such as dibutyl - tin - maleate, dibutyl - tin - laurate, di - n - octyl - tin - maleate; acrylic esters, such as ethyl -.a - cyano - β,β diphenylacrylate, methyl - a - cyano - β methyl - 4 - methoxy - cinnamate; metal salts of higher fat acids, such as calcium, barium, zinc, cadmium, lead, nickel stearates, calcium cadmium, barium, zinc laurates.

In the following several examples are described, in an illustrative and not limitative way, for illustrating the usefulness of the compounds of formula (I) obtained in examples 1-7, for the stabilization of synthetic polymers.

The results of the tests are listed in the tables and compared with tests carried out without using any stabilizer and using a known stabilizer commercially available.

Example 8 2.5 g of each of the compounds listed in table 1 below, dissolved in 100 ml of chloroform, were mixed with 1000 g polypropylene *Moplen C, manufactured by Societa Montedison, Ιθ Italy, 1 g. n-octadecyl - 3(3,5 - ditert.butyl - 4 hydroxy - phenyl)propionate and 1 g calcium stearate.

The solvent was removed in an oven under vacuum at a temperature of 50°C for 4 hours.

The dry mixture so obtained was then extruded at a la temperature of 200°C and made into granules, wherefrom 0.2 mm thick plates were produced by die-casting at 200°C.

Said plates were exposed in a Xenotest 150 apparatus at a black panel temperature of 60°C and the increase in the content of carbonyl groups was periodically determined using the not exposed specimens for balancing the polymer original absorption. The time (T 0.1) required to have, a Δ00% = 0.1 at 5.85pm was then calculated.

As a comparison, a polymer plate was produced under the same conditions, but without addition of any light stabilizer, 2b and another one with the addition of 2.5 g of 2-hydroxy-4-noctyloxybenzophenone, a usual commercial stabilizer.

*Moplen is a regd. trade mark 4384? The results are referred in Table 1.

TABLE 1 T 0.1 (hours) Stabilizer None 280 ί) 2- hy d r o xy-4-n-octyl oxybenzophenone 900 Compound of example 1 1170 Compound of example 2 1550 Compound of exaimpl e 3 1450 Compound of example 4 1780 10 Compound of example 5 1680 Compound of example 6 1600 Compound of example 7 1570 Example 9 g of each of the compounds listed in table 2 below, lo dissolved in 100 ml chloroform, were mixed with 1000 g of high density polyethylene Moplen (regd. trade mark R0, manufactured by Societa Montedison, Italy), 0.5 g of n-octadecyl-3-(3,5-di tert.butyl-4-hydroxy-phenyl) propionate and 1 g of calcium stearate.

The dry mixture so obtained was then extruded at a temperature of 190°C and made into granules, wherefrom by die casting at 200°C plates 0.2 mm thick were produced, said plates were Zb exposed in a Xenotest 150 apparatus, as in example 8. 4M47 The time T 0.06 required to haveAC0% = 0.05 at 5.85 pm was determined.

As a comparison, under the same conditions a polymer plate was produced without addition of any light stabilizer and another plate was produced with addition of 2 g of 2-hydroxy-4-n-octyloxybenzophenone.

The results are referred to in table 2.

T 0.05 (hours) TABLE 2 Stabilizer None 320 2-hydroxy-4· -n- octyloxybenzophenone 1100 Compound of example 1 1750 Compound of example 2 2300 Compound Of example 3 2080 lb Compound of example 4 2360 Compound of example 5 2210 Compound of example 6 2190 Compound of example 7 2270 Example 10 The polypropylene granules produced in example 8 were made into fibers under the following conditions: Extruder temperature Die temperature Stretching ratio Multifilament count 250-260°C 250°C 1 :4 1080/200 den.

The fibers were assembled on a white paperboard and exposed until brittleness in a Xenotest 150 at a black panel temperature of 60°C.

Another lot of the same fibers were subjected to tests of extraction fastness under the following conditions: the fibers fixed to a stainless steel frame were soaked into an aqueous solution containing 0.5% b.w. of a commercially available surfactant *Dixan, with stirring at a temperature of 80°C.

After 10 hours treating, the fibers were rinsed with distilled water, dried and exposed until brittleness to the Xenotest 150 under the same conditions as above.

As a comparison under the same conditions, polypropylene fibers were produced ahd treated with addition of a) 0.25% by weight of 2-hydroxy-4-n-octyloxybenzophenone, and b) 0.25. by weight of 2,4,6 - tris{2,2,6,6 - tetramethyl - 4 - piperidylamino) - 1,3,5, - triazine, as an example of French Patent No. 2 181 059. The results obtained, are referred to in table 3.

TABLE 3 Time to brittleness (Hours) Stabilizer Not treated fibers Treated fibers a) 670 360 b) 1080 380 Compound of example 1 950 780 Compound of example 2 1160 960 Compound of example 3 1020 810 Compound of example 4 1250 1040 Compound of example 5 1090 870 Compound of example 6 1170 920 Compound of example 7 1190 870 *Dixan is a ' Trade Mark ^3247 From the test results, a considerable increase in the time required to induce a degradation in a polymer stabilized oy the invention compounds can be observed with respect to the same polymer not stabilized.

Furthermore, clearly improved effects induced by the invention compounds can be observed in comparison with a similar proportion of a prior art additive.

It will be further appreciated from table 3 that the stabilizers of the invention maintain a very high proportion of their activity, when the stabilized fibers have been treated so as to promote the extraction thereof from the polymer, even when the polymer is in the very thin form of a fiber or film.

Claims

1. A compound having the formula (I) wherein R-| and Ry are the same or different and each is hydrogen, hydroxyl, straight or branched chain C-j to C lg alkyl, C 5 to C^ g cycloalkylj substituted or unsubstituted Cg to C^g aryl, Cy to C lg aralkyl, or a piperidine radical of formula (II) in which R 4 , Rg, Ry and R g are the same or different and each is C 1 to Cg alkyl, and R g is H, 0, C^ to C 12 alkyl, or C 2 to C-| 2 alkenyl or alkynyl, or R^ and R 2 may be 43347 in which Rg and R|g are the same or different and each is hydrogen, C-j to Cg alkyl, Cg to Cg cycloalkyl, or Cg to Cg aryl; a X and Y are the same or different and each is -0-, -S-, or — N — I R 11 R|1 being H, straight or branched chain C| to Cgg alkyl, Cg to C^g cycloalkyl, C g to C lg aryl, C ? to C 1g aralkyl or a 10 piperidine radical of formula (II); R-j-X- and R 2 -Y-, taken as a single substituent group, may be a radical of a nitrogenous heterocyclic compound having 5 to 8 ring atoms linked to the triazine ring by means of a disubstituted nitrogen atom of said radical, or R^-X- and R 2 -Y- may be lb Cl- or Br-; n is an integer from 2 to 6; Rg is an n-valent residue derived from a polyalcohol, a polymercaptan or a polyamine by reaction of the active H atoms thereof with a halogen atom of a monohalo triazine; or Rg may be R 12'( z )n’ where R i2 1S an n-valent C| to Cg g aliphatic, 20 Cg to C-jg cycloaliphatic or C g to C| g aromatic radical, and Z is -0-, -S- or R n Rn being as defined above; when n = 2, radical Rg may be a divalent radical 13«47 of a nitrogenous heterocyclic compound having 6 to 8 ring atoms, the disubstituted nitrogen atoms of which are!inked to a triazine ring; when n = 2, radical R 3 may be — N — N — ( I R 13 R 14 in which R-| 3 and R-p are the same or different, and each is hydrogen, C-j to Cp alkyl, Cg to Cp cycloalkyl, Cg to Cp aryl, Cy to Cp aralkyl, or a piperidine radical of formula (II); when n =3, ;4, 5 or 6 then R 3 may be - N~(CH 2 ) -N- jjCH 2 ) s-(CH 2 > r -t wherein Rp is as defined above, r and s are the same or different and each is an integer from 2 to 6, and t is 0, 1, 2 or 3, provided that at least one piperidine radical of formula (II) is present in at least one of the radicals R-j-X-, Rg-Y-, and Rg.

2. A compound according to claim 1, in which Rp is hydrogen, straight or branched chain Cj to Cp alkyl, C g to C-j 0 cycloalkyl, C g to Cp aryl, or a piperidine radical of formula (II).

3. A compound according to claim 1, wherein R 1 and R 2 are the same or different and each is selected from hydrogen, C 1 to C 10 alk Y 1j c 5 t0 c io cycloalkyl, C g to Cp aryl, or a piperidine radical of formula (II).

4. A compound according to claim 1, in which R^, Rg, R? and Rg are each methyl and Rg is hydrogen or methyl. 3. A compound according to claim 1, wherein Rg and R j θ are hydrogen or methyl .

5. 6 6. A compound according to claim 1, in which Rj 2 is C-| to C-j θ alkylene, Cg to Cj Q cycloalkylene, Cg to Cj Q arylene, or C? to Cj Q aralkylene.

6. 7. A compound according to claim 1, in which said divalent heterocyclic radical is piperazine-1,4-diyl. 10

7. 8. A compound according to claim 1, wherein Rj 3 and Rj 4 are hydrogen or methyl.

8. 9. A compound according to claim 1, wherein each of r and s is 2, 3 or b, t is 0 and n is 2 or 3.

9. 10. -A compound according to claim 1, in which each of 15 X, Y and Z is -0-, \NH, N-alkyl having 1 to 6 C atoms or 2 is hydrogen, Cj to Cg alkyl or 2,2,6,6-tetramethyl -4-piperidyl; R^, Rg, R ? and Rg are methyl; Rg is hydrogen; Rg and Rj 0 are hydrogen; Rjj is hydrogen, Cj to Cg alkyl 20 or 2,2,6,6-tetramethyl-4-piperidyl; and Rj 2 is C 2 to Cg alkylene.

10. 11. A compound according to claim 1, in which each of X, Y and Z is -0-, 26 Rj and R 2 is hydrogen, Cj to C g alkyl or 2,2,6,6-tetramethyl -4-piperidyl; R^, Rg, R? and Rg are methyl; Rg is hydrogen; Ry and Rjq are hydrogen; Rj j is hydrogen, Cj to Cg alkyl or 2,2,6,6-tetramethyl-4-piperidyl; and Rj 3 and Rj 4 are hydrogen.

11. 12. A compound according to claim 1, wherein each of X, Y and Z is -0-, N-Pip, Pip being 2,2,6,6-tetramethyl-4-piperidyl; each Rj and R 2 is hydrogen, C-j to C g alkyl or 2,2,6,6-tetramethyl b -4-piperidyl; R^, R g , Ry and R g are methyl; R g is hydrogen; R g and R^ g are hydrogen; Rjj is hydrogen, Cj to C g alkyl or 2,2,b,b-tetramethyl-4-piperidyl; eacn of r and s is 2 or 3, t is 0, and n is 2 or 3.

12. 13. A method for producing a compound of the formula (I) 10 as claimed in claim 1, comprising reacting a 4,6-disubstituted 2-halogen-tria2ine with a polyalcohol, a polymercaptan or a polyamine in an inert solvent, at the boiling temperature of the solvent, in the presence of an organic or inorganic base to form the corresponding compound, and recovering said lo compound from the mixture.

13. 14. A method according to claim 13, wherein the polyalcohol, polymercaptan or the polyamine has the formula R] 2 -(ZH) n> wherein R^ 2 and Z are as defined in claim 1, the molar ratio of 4,6-disubstituted-2-halogen-triazine !0 to the compound of formula Rj 2 -(ZH) n ^ e ^ n 9 n; l· lb. A method according to claim 13, wherein the polyamine has the formula UN— NH R 13 *14 wherein R^ 3 and R·^ are as defined in claim 1, the molar ratio of 4,6disubstituted-2-halogen-triazine to hydrazine being 2.Ί.

14. 16. A method according to claim 13, wherein'the polyamine has the formula HN - (CH 2 ) - NH-£(CH 2 ) —NH~|— NH-(CH 2 ) -NH R n R n wherein r, s and t are as defined in claim 1, the molar ratio of 4,b-disubstituted-2-ha1ogen-triazine to polyamine being 1 mole of the halogen-triazine per 1 amine group of polyamine, or in excess of that ratio. o

15. 17. A method for producing a compound having the i formula (I) as claimed in claim 1, comprising reacting a 6-substituted-2,4-dihalogen-l,3,5-triazine with a compound of the formula R^-XH and a compound of the formula Ry-YH, Rp 'R 2 i 'X and Y being as defined in claim 1, in a molar 10 ratio of 1:2 n, in an inert solvent, at the boiling temperature of the solvent, in the presence of an organic or inorganic base, to form the corresponding compound, and recovering said compound from the mixture.

16. 18. A method of increasing the light stability of a la synthetic polymer, comprising adding to said synthetic polymer, an amount of a compound having the formula (I) as claimed in any one of claims 1 to 12 effective to increase the light stability of said synthetic polymer.

17. 19. A method according to claim 18. wherein said synthetic

18. 20 polymer is a polyolefin. 20. A method according to claim 19, wherein said synthetic polymer is polypropylene.

19. 21. A method according to claim 19, wherein said synthetic polymer is polyethylene. 4324?

20. 22. A method according to claim 19, wherein said synthetic polymer is in the form of fibers or film.

21. 23. A method according to claim 18, wherein said compound is added to the synthetic polymer in an amount ri from 0.1 to 1% by weight of the synthetic polymer.

22. 24. A method of producing a compound of the formula (I) as claimed in claim 1, substantially as hereinbefore described in any one of Examples 1 to 7. 2b. A method as claimed in claim 18, substantially 10 as hereinbefore described in any one of Examples 8 to 10.